Manufacturing method of grating

ABSTRACT

A method for making a grating includes the following steps. A first photoresist film is formed on a substrate. A second photoresist film is applied on the first photoresist film. A number of first cavities are formed in the second photoresist film, wherein part of the first photoresist film is exposed to form a first exposed part. A number of second cavities are formed, wherein part of the surface of the substrate is exposed to form an exposed surface. A mask layer is deposited on the second photoresist film and the exposed surface of the substrate. A patterned mask layer is formed, and part of the substrate is exposed to form a second exposed part. The second exposed part of the substrate is etched through the patterned mask layer. The patterned mask layer is removed.

This application is a continuation of U.S. patent application Ser. No.14/470,814, filed on Aug. 27, 2014, entitled, “MANUFACTURING METHOD OFGRATING,” which is a continuation of U.S. patent application Ser. No.13/658,029, filed on Oct. 23, 2012, entitled, “MANUFACTURING METHOD OFGRATING,” which claims all benefits accruing under 35 U.S.C. §119 fromChina Patent Application 201110333523.4, filed on Oct. 28, 2011 in theChina Intellectual Property Office, the disclosure of which isincorporated herein by reference. The disclosures of theabove-identified applications are incorporated herein by reference.

BACKGROUND

1. Technical Field

The disclosure relates to a manufacturing method of a grating.

2. Description of Related Art

A sub-wavelength grating is a common optical component in thesemiconductor industry. The size of the sub-wavelength grating issimilar to or less than the active wavelength of the sub-wavelengthgrating. It is difficult to make a quartz grating with high density,sub-wavelength, and mark-space ratio. The sub-wavelength grating may bemade by electron beam lithography, focused ion beam lithography,deep-ultraviolet lithography, holographic lithography, and nano-imprintlithography.

In the prior art, the aspect ratio of the sub-wavelength grating is 1:1so as to limit the application field.

BRIEF DESCRIPTION OF THE DRAWINGS

The parts in the drawings are not necessarily drawn to scale, theemphasis instead being placed upon clearly illustrating the principlesof at least one embodiment. In the drawings, like reference numeralsdesignate corresponding parts throughout the various diagrams, and allthe diagrams are schematic.

FIG. 1 is a schematic diagram showing one embodiment of a manufacturingmethod of a grating.

FIG. 2 is a top-view of a patterned mask layer used in the method ofFIG. 1.

FIG. 3 is a schematic diagram showing one embodiment of a detailmanufacturing method of a grating.

FIG. 4 is a cross-sectional diagram of one cavity of the grating of FIG.1.

FIG. 5 is one embodiment of a schematic diagram of the grating.

FIGS. 6 and 7 are pictures of the grating taken by a scanning electronmicroscope.

FIG. 8 is another embodiment of a schematic diagram of a grating.

DETAILED DESCRIPTION

Reference will now be made to the drawings to describe various inventiveembodiments of the present disclosure in detail, wherein like numeralsrefer to like elements throughout.

Referring to FIG. 1, one embodiment of a manufacturing method of agrating 10 includes the following steps. The grating 10 can be asub-wavelength grating.

In step S100, a substrate 110 is provided, and a patterned mask layer120 is formed on a surface of the substrate 110.

The substrate 110 can be a circular plate, a square plate, or any othershape plate. The substrate 110 may be a semiconductor substrate or asilicon substrate. The material of the substrate 110 may be galliumnitride (GaN), gallium arsenide (GaAs), sapphire, aluminum oxide,magnesium oxide, silicon, silica, silicon nitride, or silicon carbide,wherein the silica may form a quartz substrate or a glass substrate. Inthe embodiment, the substrate 110 is a quartz substrate.

In addition, the patterned mask layer 120, which is made by aphotoresist film, has a plurality of mask strips 124 and a plurality offirst nanometer scale cavities 122 arranged in intervals. A part of thesurface of the substrate 110 is exposed to the patterned mask layer 120through the first cavities 122. The nano-pattern of the patterned masklayer 120 can be a continuous pattern or a discontinuous pattern. In theembodiment, the material of the patterned mask layer 120 is chromium,the mask strips 124 and the first cavities 122 are arranged with regularintervals, the width of each first cavity 122 is about 100 nm, and thedepth of each cavity 122 is about 40 nm.

In step S200, the substrate 110 with the patterned mask layer 120 isplaced in a microwave plasma system (not shown), and an etching gas 130having carbon tetrafluoride (CF₄), sulfur hexafluoride (SF₆) and argon(Ar₂) is guided into the microwave plasma system to etch the substrate110 exposed to the patterned mask layer 120.

In step S300, the patterned mask layer 120 is removed to obtain agrating 10 having a high aspect-ratio. In the embodiment, the highaspect-ratio is equal to or greater than 6:1.

Referring to FIG. 3, the method for making the patterned mask layer 120on the substrate 110 includes the following steps.

In step S110, a photoresist film 141 is disposed on the surface of thesubstrate 110. The photoresist film 141 for protecting the substrate 110can be a single layer or a multi-layer film. The material of the singlelayer may be ZEP520A, hydrogen silsesquioxane (HSQ), Polystyrene (PS),Polymethylmethacrylate (PMMA), AR-N series, AR-Z series, AR-B series,SAL-601, or organic silicon oligomer. In one embodiment, the photoresistfilm 141 is a two layer structure. The material of one layer of thephotoresist film 141 is PMMA and the other layer is hydrogensilsesquioxane (HSQ), wherein the PMMA layer is disposed adjacent to thesubstrate 110.

Step S110 can further include the steps S112 to S118.

In step S112, the substrate 110 is cleaned according to cleanroomstandards.

In step S114, the PMMA layer is formed on the surface of the substrate110 by spin coating. The thickness of the PMMA layer is in the range ofabout 100 nm to about 500 nm.

In step S116, a transitional layer is formed to cover the PMMA layer bysputtering or depositing. In the embodiment, the material of thetransitional layer is silica, which is deposited on the PMMA layer. Thethickness of the transitional layer is in the range of about 10 nm toabout 100 nm.

In step S118, the HSQ layer is formed to cover on the transitional layerby bead coating or spin coating. In the embodiment, the HSQ layer isformed on the transitional layer by spin coating with high pressure. Thethickness of the HSQ layer is in the range of about 100 nm to about 500nm, and preferably in the range of about 100 nm to about 300 nm.

In step S120, a nano-pattern is formed on the photoresist film 141 bynano-imprint lithography. A plurality of protrusions 142 and a pluralityof cavities 144 are formed on the photoresist film 141. Step S120 canfurther include the steps S122 to S126.

In step S122, a mold with a nano-pattern is provided, wherein thenano-pattern is disposed on a surface of the mold. The nano-patternincludes a plurality of protrusions and a plurality of cavities. Eachcavity is defined between two protrusions. In the embodiment, the moldis a transparent material, which may be made of silica, quartz, ordiboride glass.

In step S124, the surface with the nano-pattern of the mold is attachedto the HSQ layer of the photoresist film 141, and a force is provided tomap the nano-pattern from the mold to the photoresist film 141 undernormal atmospheric temperature. In one embodiment, the nano-pattern isonly formed at the HSQ layer, and the PMMA is intact.

In step S126, the mold is removed from the substrate 110 so as to formthe protrusions 142 and the cavities 144 on the photoresist film 141.The protrusions 142 correspond to the cavities of the mold, and thecavities 144 corresponding to the protrusions of the mold.

In step S130, the photoresist film 141 located at the cavities 144 areremoved to form a patterned photoresist layer 140 with a plurality ofsecond cavities 146. A part of the surface of the substrate 110 isexposed to the patterned photoresist layer 140 through the second cavity146. Step S130 can further include steps S132 and S134.

In step S132, the substrate 110 is placed in a microwave plasma system,and a reaction gas CF₄ is guided into the microwave plasma system toremove the HSQ layer located at the cavities 144. The microwave plasmasystem is operated in reaction-ion-etching (RIE) mode. During the RIEmode, an induced power source generates CF₄ plasma, wherein the CF₄plasma with low ion energy is diffused from the generation area to thesurface of the substrate 110 to etch the HSQ layer located at thecavities 144. During the process, the power of the microwave plasmasystem is about 40 watts (W), the volume flow of the CF₄ plasma is about26 sccm, the pressure in the microwave plasma system is about 2 pascal(pa), and the etching time is about 10 seconds. The HSQ layer located atthe cavities 144 is removed and a part of the PMMA layer is exposedafter above process. The thickness of the HSQ layer located at theprotrusions is reduced after the step S132.

In step S134, a reaction gas O₂ is guided into the microwave plasmasystem to remove the PMMA layer located at the cavities 144 to form aplurality of second cavities 146 to expose a part of the surface ofsubstrate 110. During the process, the power of the microwave plasmasystem is about 40 W, the volume flow of the O₂ plasma is about 40 sccm,the pressure in the microwave plasma system is about 2 pa, and theetching time is about 120 seconds. The HSQ layer can be a mask duringthe process of removing the PMMA layer to increase etching precision. Inone embodiment, the depth of one of the second cavity 146 is in therange of about 100 nm to about 500 nm and the width of one of the secondcavity 146 is in the range of about 25 nm to about 150 nm.

In step S140, a mask layer 121 is deposited on the patterned photoresistlayer 140 and the surface of the substrate 110 exposed to the patternedphotoresist layer 140. A mask layer 121 is formed on the patternedphotoresist layer 140 and the surface of the substrate 110 exposed tothe second cavities 146. The material of the mask layer 121 can bechromium, and the thickness of the mask layer 121 is about 40 nm.

In step S150, the patterned photoresist layer 140 and the mask layer 121on the protrusions are removed to form a patterned mask layer 120. Thepatterned photoresist layer 140 can be removed by Tetrahydrofuran (THF),acetone, methyl ethyl ketone, cyclohexane, n-hexane, methyl alcohol, orethyl alcohol. The mask layer 121 covered on the patterned photoresistlayer 140 is also removed with the patterned photoresist layer 140 toform the patterned mask layer 120. The patterned mask layer 120 isformed on the surface of the substrate. In one embodiment, the patternedphotoresist layer 140 and the mask layer 121 thereon is removed byultrasonic cleaner and acetone.

Another method for making the patterned mask layer includes the steps offorming a chromium layer on the surface of the substrate 110, forming aphotoresist on a surface of the chromium layer, patterning thephotoresist by photolithography to expose a part of the chromium layer,removing the chromium layer exposed to the photoresist by electron beambombardment, and removing the photoresist to form a patterned chromiumlayer. The patterned chromium layer can be the patterned masked layer.

The mark-space ratio of the patterned mask layer 120 is 1:1, and thewidth of the first cavity 122 is in the range of about 25 nm and about150 nm.

In step S200, the microwave plasma system is operated under RIE mode.The etching gases include CF₄, SF₆, and Ar₂, which are generated by aninduced power source of the microwave plasma system. During the etchingprocess, the CF₄ and SF₆ etching gas easily react with the substrate 110to produce a silicon fluoride compounds. The silicon fluoride compoundscan easily adhere to the exposed surface of the substrate 110 to blockthe substrate 110 etched by the etching gas of CF₄ and SF₆. However, thebombardment of the Ar₂ etching gas can decompose the silicon fluoridecompounds so that the CF₄ and SF₆ etching gases can etch the substrate110 again to obtain the cavity with greater depth.

The volume flow of the etching gases is in the range of about 40 sccmand about 120 sccm, wherein the flow volume of CF₄ is in the range ofabout 1 sccm and about 50 sccm, the flow volume of SF₆ is in the rangeof about 10 sccm and about 70 sccm, and the flow volume of Ar₂ is in therange of about 10 sccm and about 20 sccm. In one embodiment, the flowvolume of the etching gas is about 70 sccm.

The etching gas further includes O₂, and the flow volume of O₂ is in therange of greater than 0 sccm to about 10 sccm. The etching gases of CF₄,SF₆, Ar₂, and O₂ are guided into the microwave plasma systemsimultaneously to assist the burning of the silicon fluoride compounds.In addition, the reaction between the substrate 110 and O₂ produces achemical compound having silicon-oxygen bond and silicon-carbon bond,which is burned by Ar₂ to speed up the etching time.

Referring to FIG. 4, the different flow volume of the etching gasproduces the different shape of the cavities. The cross-section of thecavity is V-shaped if the flow volume of the etching gases are less than40 sccm. The cross-section of the cavity is a U-shaped if the flowvolume of the etching gases are greater than 120 sccm. The wall of thecavity is about perpendicular to the surface of the substrate 110 whenthe flow volume of the etching gases are in the range of about 40 sccmand about 120 sccm.

In addition, a pressure of the etching gases is in the range of about 1pa to about 5 pa, and an etching power is in the range of about 40 W toabout 200 W. In the embodiment, the flow volume of CF₄ is about 40 sccm,the flow volume of SF₆ is about 26 sccm, the flow volume of Ar₂ is about10 sccm, the pressure of the etching gases is about 2 pa, and theetching power is about 70 W. Under the above condition, the etchingdepth is about 600 nm when the etching time is about 8 mins, and theetching depth is about 750 nm when the etching time is about 10 mins.

The step S300 can further include steps S302 and S304 if the material ofthe patterned mask layer 120 is chromium.

In step S302, a chromium etchant (K3[Fe(CN)6]) is provided, wherein theconcentration of the K3[Fe(CN)6] is in the range of about 0.06 mol/L andabout 0.25 mol/L.

In step S304, the substrate 110 is dipped in the chromium etchant forabout 4 mins to about 15 mins to remove the patterned mask layer 120.

The present disclosure provides has many advantages. The siliconfluoride compounds can be bombarded by Ar₂ to continue the etchingprocess to obtain the grating 10 with a high aspect ratio greater thanor equal to 6:1. The flow volume of the etching gas is controlled in therange of about 40 sccm to about 120 sccm to ensure the wall of thecavities of the substrate 110 is substantially perpendicular. The widthand the depth of the cavities of the substrate 110 can be controlledunder a particular condition. One condition includes CF₄, SF₆, and Ar₂etching gases flowing in the range of about 40 sccm to about 120 sccm,the pressure of the etching gas is in the range of about 1 pa to about 5pa, and the etching power of the microwave plasma system is in the rangeof about 40 W and about 200 W.

Referring to FIGS. 5 to 7, the grating 10 manufactured by the abovemethod includes the substrate 110. A plurality of protrusions 150 areformed on the surface of the substrate 110. A cavity 160 is formedbetween every two adjacent protrusions 150. Each of the protrusions 150has the same size and shape, and each of the cavities 160 has the samesize and shape. In addition, the protrusions 150 and the cavities 160have the same extension direction. Each of the protrusion 150 has twoopposite sidewalls, which are about perpendicular to the surface of thesubstrate 110.

The substrate 110 can be a semiconductor substrate or a silicon-basesubstrate. The material of the substrate may be gallium nitride (GaN),gallium arsenide (GaAs), sapphire, aluminum oxide, magnesium oxide,silicon, silica, silicon nitride, silicon carbide, quartz, or glass. Inthe embodiment, the material of the substrate is quartz. In addition,the material of the substrate 110 also may be a P-type semiconductor oran N-type semiconductor, e.g. P-type GaN or N-type GaN. Furthermore, thesize, the thickness, and the shape of the substrate are not limited.

Referring to FIG. 5, the length of the protrusion 150 and the cavity 160is the dimension along the Y axis, the width of the protrusion 150 andthe cavity 160 is the dimension along the X axis, the height of theprotrusion 150 is the dimension along the Z axis, and the depth of thecavity 160 is the dimension along the Z axis. The width of theprotrusion 150 is defined as W1, the width of the cavity 160 is definedas W2, and the depth of the cavity 160 is defined as D1. The ratio of W1and W2 is defined as a mark-space ratio of the grating 10. The ratio ofD1 and W2 is defined as an aspect ratio of the cavity 160. The sum ofthe W1 and W2 is defined as a duty cycle C1 of the grating 10.

The width W1 of the protrusion 150 is in the range of 25 nm to 150 nm.The depth D1 of the cavity 160 is in the range of about 150 nm to about900 nm. The width W2 of the cavity 160 is in the range of about 25 nm toabout 150 nm. The mark-space ratio is about 1:1. The aspect ratio(D1/W2) is in the range of 6:1 and 8:1. The duty cycle C1 of the grating10 is in the range of about 50 nm to about 300 nm.

In the embodiment, the width W1 of the protrusion 150 is about 100 nm.The depth D1 of the cavity 160 is about 600 nm. The width W2 of thecavity 160 is about 100 nm. The mark-space ratio is about 1:1. Theaspect ratio is about 6:1. The duty cycle C1 of the grating 10 is about200 nm.

In other embodiments, the parameter can be changed according to thedifferent conditions.

In Example 1, the width of the protrusion W1 150 is about 150 nm.

The depth D1 of the cavity 160 is about 900 nm. The width W2 of thecavity 160 is about 100 nm. The mark-space ratio is about 1:1. Theaspect ratio is about 6:1. The duty cycle C1 of the grating 10 is about300 nm.

In Example 2, the width W1 of the protrusion 150 is about 100 nm. Thedepth D1 of the cavity 160 is about 800 nm. The width W2 of the cavity160 is about 100 nm. The mark-space ratio is about 1:1. The aspect ratiois about 8:1. The duty cycle C1 of the grating 10 is about 200 nm.

In Example 3, the width W1 of the protrusion 150 is about 50 nm. Thedepth D1 of the cavity 160 is about 300 nm. The width W2 of the cavity160 is about 50 nm. The mark-space ratio is about 1:1. The aspect ratiois about 6:1. The duty cycle C1 of the grating 10 is about 100 nm.

In Example 4, the width W1 of the protrusion 150 is about 120 nm. Thedepth D1 of the cavity 160 is about 720 nm. The width W2 of the cavity160 is about 120 nm. The mark-space ratio is about 1:1. The aspect ratiois about 6:1. The duty cycle C1 of the grating 10 is about 320 nm.

In Example 5, the width W1 of the protrusion 150 is about 130 nm.

The depth D1 of the cavity 160 is about 780 nm. The width W2 of thecavity 160 is about 130 nm. The mark-space ratio is about 1:1. Theaspect ratio is about 6:1.

Referring to FIG. 8, another embodiment with a grating 20 includes asubstrate 210. The substrate 210 has a plurality of cavities 260. Thecavities 260 are parallel to each other and surrounded by a protrusion250.

The distance between the two cavities 260 is defined as W11, the widthof the cavity 260 is defined as W21, and the depth of the cavity 260 isdefined as D2. The ratio of W11 and W21 is defined as a mark-space ratioof the grating 20. The ratio of D2 and W21 is defined as an aspect ratioof the cavity 260. The sum of the W11 and W21 is defined as a duty cycleC2 of the grating 20.

The distance W11 between the two cavities 260 is in the range of about25 nm to about 150 nm. The depth D2 of the cavity 260 is in the range ofabout 150 nm to about 900 nm. The width W21 of the cavity 260 is in therange of about 25 nm and to 150 nm. The mark-space ratio is about 1:1.The aspect ratio (D2/W21) is greater than or equal to about 6:1. Theduty cycle C2 of the grating 20 is in the range of about 50 nm to about300 nm.

In summary, the width of the cavity of the grating is in the range ofabout 25 nm to about 150 nm, the aspect ratio is greater than or equalto 6:1 so that the grating of the disclosure is a sub-wavelength gratingwith high density, high aspect ratio, high mark-space ratio, highdiffraction efficiency, and low scattering.

Even though numerous characteristics and advantages of certain inventiveembodiments have been set out in the foregoing description, togetherwith details of the structures and functions of the embodiments, thedisclosure is illustrative only. Changes may be made in detail,especially in matters of arrangement of parts, within the principles ofthe present disclosure to the full extent indicated by the broad generalmeaning of the terms in which the appended claims are expressed.

What is claimed is:
 1. A manufacturing method of a grating, the methodcomprising: forming a first photoresist film on a surface of asubstrate; applying a second photoresist film on a surface of the firstphotoresist film away from the substrate; forming a plurality of firstcavities in the second photoresist film by nanoimprinting the secondphotoresist film, wherein part of the first photoresist film is exposedthrough the plurality of first cavities to form a first exposed part;forming a plurality of second cavities by etching the first exposed partof the first photoresist film, wherein part of the surface of thesubstrate is exposed through the plurality of second cavities to form anexposed surface; depositing a mask layer on the second photoresist filmand the exposed surface of the substrate; forming a patterned mask layerby removing the first photoresist film, the second photoresist film, anda portion of the mask layer deposited on the second photoresist film,wherein the patterned mask layer defines a plurality of third cavities,and part of the substrate is exposed through the plurality of thirdcavities to form a second exposed part; etching the second exposed partof the substrate through the patterned mask layer by reactive ionetching, wherein etching gases used in the reactive ion etchingcomprises carbon tetrafluoride, sulfur hexafluoride and argon; andremoving the patterned mask layer.
 2. The manufacturing method of claim1, wherein sidewalls of the plurality of second cavities in the firstphotoresist film are perpendicular with the surface of the substrateduring etching the first photoresist film.
 3. The manufacturing methodof claim 1, wherein the substrate comprises a substrate material that isselected from the group consisting of gallium nitride, gallium arsenide,sapphire, aluminum oxide, magnesium oxide, silicon, silica, siliconnitride, silicon carbide, quartz, and glass.
 4. The manufacturing methodof claim 1, wherein the mask layer comprises chromium.
 5. Themanufacturing method of claim 1, wherein a flow volume of the etchinggases is in a range of about 40 sccm to about 120 sccm.
 6. Themanufacturing method of claim 5, wherein the flow volume of the etchinggases is about 70 sccm.
 7. The manufacturing method of claim 5, whereina flow volume of carbon tetrafluoride is in a range of about 1 sccm toabout 50 sccm, a flow volume of sulfur hexafluoride is in a range ofabout 10 sccm to about 70 sccm, and a flow volume of argon is in a rangeof about 10 sccm to about 20 sccm.
 8. The manufacturing method of claim7, wherein the flow volume of carbon tetrafluoride is about 40 sccm, theflow volume of sulfur hexafluoride is about 26 sccm, and the flow volumeof argon is about 10 sccm.
 9. The manufacturing method of claim 7,wherein the etching gases further comprise oxygen, and a flow volume ofoxygen is in a range of greater than 0 sccm to about 10 sccm.
 10. Themanufacturing method of claim 9, wherein the carbon tetrafluoride, thesulfur hexafluoride, the argon, and the oxygen are guided into amicrowave plasma system simultaneously.
 11. The manufacturing method ofclaim 1, wherein an etching power is in a range of about 40 watts toabout 200 watts in the reactive ion etching.
 12. The manufacturingmethod of claim 1, wherein a pressure of the etching gases is in a rangeof 1 pascal to 5 pascal.
 13. The manufacturing method of claim 1,wherein the first photoresist film comprises polymethylmethacrylate, andthe second photoresist film comprises hydrogen silsesquioxane.
 14. Themanufacturing method of claim 1, wherein the patterned mask layer isretained on the first exposed part the substrate after removing thefirst photoresist film, the second photoresist film, and the portion ofthe mask layer deposited on the second photoresist film.
 15. Themanufacturing method of claim 1, wherein the mask layer covers thesecond photoresist film and entire the exposed surface of the substrateat the same time.
 16. A manufacturing method of a grating, the methodcomprising: applying a photoresist film on a surface of a substrate;forming a plurality of cavities and a plurality of protrusions byetching the photoresist film, wherein the surface of the substrate isexposed through the plurality of cavities to form a first exposedsurface; applying a mask layer to cover the plurality of protrusions andthe first exposed surface of the substrate, wherein the first exposedsurface is entirely covered by the mask layer; forming a patterned masklayer by removing the plurality of protrusions and a portion of the masklayer coated on the plurality of protrusions; etching the substrate byguiding etching gases comprising carbon tetrafluoride, sulfurhexafluoride, and argon into a microwave plasma system simultaneously;and removing the patterned mask layer.
 17. The manufacturing method ofclaim 16, wherein the patterned mask layer defines a plurality of secondcavities, and the surface of the substrate is exposed through theplurality of second cavities to form a second exposed surface.
 18. Themanufacturing method of claim 17, wherein a plurality of third cavitiesis defined in the substrate by etching the second exposed surface duringetching the substrate.
 19. The manufacturing method of claim 17, whereinthe mask layer covers the plurality of protrusions and entire the firstexposed surface of the substrate at the same time.
 20. The manufacturingmethod of claim 17, wherein the patterned mask layer is restrained onthe first exposed surface after removing the plurality of protrusionsand the portion of the mask layer coated on the plurality ofprotrusions.